阅读说明：本技术 芳香族重氮盐、表面改质的载体、复合材料与其形成方法 (Aromatic diazonium salt, surface-modified carrier, composite material and forming method thereof ) 是由 张嘉文 张信贞 潘益宗 余若涵 徐崇桓 杨智超 周力行 陈哲阳 于 2019-07-08 设计创作，主要内容包括：芳香族重氮盐、表面改质的载体、复合材料与其形成方法。一种表面改性的载体,包括：载体；以及起始剂,接枝至载体的表面,其中起始剂的结构为：<Image he="311" wi="695" file="DDA0002122101900000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R<Sup>1</Sup>为-O-或-NH-；R<Sup>2</Sup>为<Image he="177" wi="700" file="DDA0002122101900000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>或上述的组合,其中R<Sup>3</Sup>为H或甲基,R<Sup>4</Sup>为H、C<Sub>1-18</Sub>的直链烷基、C<Sub>1-18</Sub>的支链烷基、<Image he="149" wi="413" file="DDA0002122101900000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="74" wi="700" file="DDA0002122101900000014.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="61" wi="700" file="DDA0002122101900000015.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="103" wi="307" file="DDA0002122101900000016.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>或<Image he="134" wi="278" file="DDA0002122101900000017.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中a为1至15,且R<Sup>5</Sup>为H或甲基；以及n为0至100。(Aromatic diazonium salts, surface-modified carriers, composites and methods of forming the same. A surface-modified support comprising: a carrier; and an initiator grafted to the surface of the support, wherein the initiator has the structure: wherein R is 1 is-O-or-NH-; r 2 Is composed of Or combinations of the foregoing, wherein R 3 Is H or methyl, R 4 Is H, C 1‑18 Straight chain alkyl group of (1), C 1‑18 A branched alkyl group of, Or Wherein a is 1 to 15, and R 5 Is H or methyl; and n is 0 to 100.)

1. An aromatic diazonium salt having the structure:

wherein R is¹is-O-or-NH-; and

is Cl^-、Br^-、BF₄ ^-Or CF₃SO₃ ^-。

2. A surface-modified support comprising:

a carrier; and

an initiator grafted to the surface of the support,

wherein the structure of the initiator is:

wherein R is¹is-O-or-NH-;

R²is composed ofOr combinations of the foregoing, wherein R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, and R⁵Is H or methyl; and

n is 0 to 100.

3. The surface modified support of claim 2, wherein the support comprises a metal, ceramic, or plastic.

4. The surface modified carrier of claim 3, wherein the metal comprises tool steel, soft magnetic, stainless steel, or an alloy.

5. A composite material, comprising:

a surface-modified support comprising:

a carrier; and

an initiator or a functional group grafted to the surface of the support,

wherein the initiator has the structureR¹is-O-or-NH-; r²Is composed ofOr a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100;

wherein the functional group has the structureAnd R is⁶Is H or C_1-10A linear or branched alkyl group of (a); and

a polymer coating the surface modified carrier.

6. The composite material of claim 5, wherein the polymer comprises polyamide, polyurethane, polyvinylidene fluoride, polyoxymethylene, polyethylene, polypropylene, polystyrene, polylactic acid, polycarbonate, acrylonitrile-butadiene-styrene copolymer, or a combination thereof.

7. The composite material of claim 5, wherein the carrier comprises a metal, ceramic, or plastic.

8. The composite material of claim 7, wherein the metal comprises tool steel, soft magnetic, stainless steel, or an alloy.

9. A method of forming a composite material, comprising:

mixing 100 parts by weight of a surface-modified carrier, 1 to 10 parts by weight of a polymer, and 25 to 200 parts by weight of a solvent to form the composite material,

wherein the surface-modified carrier comprises:

a carrier; and

an initiator or a functional group grafted to the surface of the support,

wherein the structure of the initiator is:R¹is-O-or-NH-, R²Is composed ofOr a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100;

wherein the functional group has the structureAnd R is⁶Is H or C_1-10A linear or branched alkyl group of (a);

wherein the polymer coats the surface-modified carrier.

10. The method of claim 9, wherein the step of mixing 100 parts by weight of the surface-modified carrier, 1 to 10 parts by weight of the polymer, and 25 to 200 parts by weight of the solvent further comprises more than 0 and less than 100 parts by weight of water.

11. The method of claim 9, wherein the solvent comprises phenol, ethanol, ethylene glycol, propylene glycol, benzyl alcohol, butyl diglycol ether, diethyl diglycol ether, butyl glycol ether, n-decanol, or combinations thereof.

12. The method of claim 9, wherein the polymer comprises polyamide, polyurethane, polyvinylidene fluoride, polyoxymethylene, polyethylene, polypropylene, polystyrene, polylactic acid, polycarbonate, acrylonitrile butadiene styrene copolymer, or combinations thereof.

13. The method of forming a composite material of claim 9, wherein the carrier comprises a metal, ceramic, or plastic.

14. The method of forming a composite material of claim 13, wherein the metal comprises tool steel, soft magnetic, stainless steel, or an alloy.

Technical Field

The present invention relates to the field of methods for modifying the surface of a support, and more particularly to aromatic diazonium salts for use in modifying the surface of a support.

Background

The 3D printing rapid forming technology is a technology which applies adhesive materials such as powdered metal or plastic and the like and constructs an object in a mode of stacking and accumulating layer by layer, has simple, rapid, digital and additive processes, does not need plate making and can manufacture products with special configurations, wherein the Binder Jetting 3D printing cannot be popularized at present, and is a very key problem, and is lack of materials of various plastics or polymers for coating metal powder.

Disclosure of Invention

One embodiment of the present invention provides an aromatic diazonium salt having the structure:

wherein R is¹is-O-or-NH-; andis Cl^-、Br^-、BF₄ ^-Or CF₃SO₃ ^-。

One embodiment of the present invention provides a surface-modified carrier, comprising: a carrier; and an initiator grafted to the surface of the support, wherein the initiator has the structure:wherein R is¹is-O-or-NH-; r²Is composed ofOr combinations of the foregoing, wherein R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, and R⁵Is H or methyl; and n is 0 to 100.

An embodiment of the present invention provides a composite material, including: a surface-modified support comprising: a carrier; and an initiator or functional group grafted to the surface of the support, wherein the initiator has the structure:R¹is-O-or-NH-, R²Is composed of Or a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100; wherein the functional group has the structureAnd R is⁶Is H or C_1-10A linear or branched alkyl group of (a); and a polymer coating the surface-modified support.

An embodiment of the present invention provides a method for forming a composite material, including: mixing 100 parts by weight of a surface-modified carrier, 1 to 10 parts by weight of a polymer, and 25 to 200 parts by weight of a solvent to form a composite material, wherein the surface-modified carrier comprises: a carrier; and an initiator grafted to the surface of the support, wherein the initiator has the structure:R¹is-O-or-NH-; r²Is composed ofCombinations of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100; wherein the functional group has the structureAnd R is⁶Is H or C_1-10A linear or branched alkyl group of (a); wherein the polymer coats the surface-modified support.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.

An embodiment of the present invention provides an aromatic diazonium salt, which has a structure:

wherein R is¹is-O-or-NH-; andis Cl^-、Br^-、BF₄ ^-Or CF₃SO₃ ^-. For example, the aromatic diazonium salt may be prepared from a p-aminobenzene derivative, an acid (HA, such as HCl, HBr, HBF)₄Or CF₃SO₃H) With NaNO₂After the reaction, an aromatic diazonium salt is formed. In one embodiment, the above reaction may be as follows:

wherein R is¹is-O-or-NH-.

The aforementioned aromatic diazonium salts may be used to modify the surface of an object and as an initiator (initiator), for example, the aforementioned aromatic diazonium salts may be dissolved in a suitable solventAfter contacting the support for a period of time to graft the aromatic diazonium salt (initiator) onto the support to form a surface modified support. In one embodiment, the weight ratio of the aromatic diazonium salt to the carrier may be between 1: 15 and 1: 2. If the ratio of the aromatic diazonium salt is too low, the amount of the initiator grafted to the surface of the carrier becomes insufficient, and the amount of the polymer-coated surface-modified carrier to be coated cannot be increased effectively (see below). If the proportion of aromatic diazonium salt is too high, it will only increase the cost if the surface of the support cannot be further modified. In one embodiment, after the aromatic diazonium salt (initiator) is grafted onto the surface of the support, the aromatic diazonium salt may be further polymerized with a monomer having a double bond to extend the chain length of the initiator. In summary, the surface-modified support may comprise: a support, and an initiator grafted to the surface of the support; the structure of the above initiator may be:wherein R is¹is-O-or-NH-; r²Is composed of Or a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100. Before the subsequent polymerization has not taken place, n is 0, i.e.the starter has the structureIf the surface is grafted withThe carrier is added with a monomer with double bonds for polymerization reaction, and then the structure of the initiator isAnd R is²The corresponding monomer species, for example, the monomer can be styrene, acrylic acid, methacrylic acid, acrylate, methacrylate, acrylamide, methacrylamide, acrylonitrile, the like, or combinations of the foregoing. The polymerization reaction may be carried out, for example, by adding a monomer for polymerization for a certain period of time and then adding another monomer for polymerization for a certain period of time to form a block copolymer. In another embodiment, different monomers may be added simultaneously to the reaction to form a random copolymer. It is to be noted that the polymerization may be carried out after the initiator has been grafted onto the support surface. If the aromatic diazonium salt is taken directly for polymerization, it is difficult to graft the initiator containing the polymer segment onto the support surface afterwards, since the aromatic diazonium salt may be reacted away when the polymerization is carried out. In one embodiment, the weight ratio of the support surface grafted with initiator to the monomers subsequently polymerized to form the polymer segment is between 1: 1.5 and 1: 5. If the proportion of monomers is too low, the chain length of the initiator is insufficient and insufficient hydrogen bonds with the subsequently mentioned polymers are produced, resulting in a decrease in the coating amount of the polymer-coated surface-modified carrier.

In some embodiments, the carrier comprises a metal, ceramic, or plastic. For example, metals include tool steels, soft magnets, stainless steels, or alloys; the ceramic comprises zirconia, zirconium beads, alumina, silicon oxynitride, silicon carbide, or barium titanate; plastics include nylon, polyethylene, polyvinyl chloride, polystyrene, polyester, polyurethane, polybutylene terephthalate, polymethyl methacrylate, polyoxymethylene, polycarbonate, or polyethylene terephthalate. The carrier can be in the shape of powder, sheet, block, hole or other suitable shapes. In one embodiment, the carrier is a powder. In one embodiment, the particle size of the powder is between 10 microns and 400 microns. If the particle size of the powder is too small, the specific surface area increases, the molecular attraction between the powders increases, and the fluidity decreases, which is not favorable for the use of an operation machine for 3D printing. If the particle size of the powder is too large, voids may occur between the powders after printing, which may affect the bending strength of the molded article. It is noted that the particle size range of the powder is for specific applications such as 3D printing. The carrier is not limited to the above dimensions if it is used in other fields.

An embodiment of the present invention provides a composite material, including: a surface-modified support, and a polymer coating the surface-modified support. The surface-modified support comprises: a carrier; and an initiator or functional group grafted to the surface of the support. The structure of the initiator is:wherein R is¹is-O-or-NH-, R²Is composed ofOr a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100. The structure of the functional group isAnd R is⁶Is H or C_1-10Linear or branched alkyl groups of (a). The hydrogen bonds are formed between the polymer and the initiator or functional groups grafted on the surface of the carrier, so that the proportion of the polymer coated on the carrier can be further increased. For example, the polymer comprises a polyamidePolyurethane, polyvinylidene fluoride, polyoxymethylene, polyethylene, polypropylene, polystyrene, polylactic acid, polycarbonate, acrylonitrile-butadiene-styrene copolymer, or combinations thereof. In this embodiment, the type of carrier is similar to that described above and will not be described herein.

In one embodiment, the method for forming the composite material includes: the surface-modified carrier is coated with a polymer by mixing 100 parts by weight of the surface-modified carrier, 1 to 10 parts by weight of the polymer, and 25 to 200 parts by weight of a solvent to form a composite material. If the proportion of the polymer is too low, the thickness of the polymer-coated surface-modified carrier is insufficient, and 3D printing cannot be effectively welded and molded. If the proportion of the polymer is too high, a plurality of carriers are likely to be coated at the same time, and the particle diameter of the carrier becomes large. If the proportion of the solvent is too low, the polymer cannot be dissolved efficiently. If the proportion of the solvent is too high, the coated carrier is not easily precipitated.

The above surface-modified support comprises: a carrier; and an initiator or functional group grafted to the surface of the support. The structure of the initiator is:wherein R is¹is-O-or-NH-, R²Is composed ofOr a combination of the foregoing, R³Is H or methyl, R⁴Is H, C_1-18Straight chain alkyl group of (1), C_1-18A branched alkyl group of, Wherein a is 1 to 15, R⁵Is H or methyl, and n is 0 to 100. The structure of the functional group isAnd R is⁶Is H or C_1-10Linear or branched alkyl groups of (a).

In some embodiments, a method of forming a composite, wherein the step of mixing 100 parts by weight of the surface-modified carrier, 1 to 10 parts by weight of the polymer, and 25 to 200 parts by weight of the solvent further comprises greater than 0 and less than 100 parts by weight of water. Water can reduce the amount of solvent used and help the polymer to precipitate out of the coated carrier. If the amount of water is too large, the polymer precipitates too quickly to effectively coat the carrier. For example, the surface-modified carrier, the polymer, the solvent, and the water may be mixed thoroughly, heated to about 140 ℃ to 170 ℃ in a high pressure reaction tank (at a pressure between 60psi and 120 psi) for about 0.5 to 1 hour, and then slowly cooled to remove the solvent and the water, thereby obtaining the composite material.

In some embodiments, the solvent comprises phenol, ethanol, ethylene glycol, propylene glycol, benzyl alcohol, diethylene glycol butyl ether, diethylene glycol ethyl ether, n-decanol, ethylene glycol monobutyl ether, or combinations thereof. In this embodiment, the types of polymer, carrier, and metal are similar to those described above and will not be repeated here.

In summary, the aromatic diazonium salt provided by the embodiments of the present invention can effectively modify the surface of the carrier, and can be used as an initiator, which can further perform a polymerization reaction with the monomer to increase the chain length. The initiator or functional group on the surface of the support may have hydrogen bonding with other polymers to increase the amount of coating of the surface modified support by the other polymers. When the carrier is powder, the composite material can be used in 3D printing.

In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below: